Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CATALYST A~l~D METHODS
-
Back round of the Invention
g
Catalysts for polymerizing and copolymerizing
olefins have been known and are widely used in indus-
try. The catalysts of this invention have many super-
ior properties over prior catalysts in that they
are adaptable to low pressure, vapor phase, solution
form or, most importantly, particle form processes
of polymerizing. When used in a continuous particle
form ethylene polymerization process, these catalysts
display excellent melt index control of resulting
polymers and copolymers because of their extraordinary
sensitivity to hydrogen.
This extraordinary sensitivity to hydrogen
can in part be achieved by adjusting the concentra-
tions of catalyst components on the support while
maintaining a constant molar ratio between them. As
a result, polymers and copolymers-can be produced with-
in a preselected melt index range.
The most important prior art of which Appli-
cant is aware is U.S. Patent 3,981,725 which describes
the use of silica as a finely divided support for
Ziegler-type catalyst compounds.
Another U.S. Patent is 4,173,547 which dis-
closes the use of a?umina and silica as such a support,
: French Demande 2,406,643 disc].oses a polyeth-
ylene catalyst comprising a reaction product of dibu-
tylmagnesium, ethylaluminum sesquichloride and ~etra-
isopropyl titanate.
U.5. Patent 4,173,547 discloses the use of a
dibutylmagnesium with alumina or silica in a poly-
merization catalyst.
German Offen. 2,523,165 discloses a catalyst
prepared by the reaction of a dibutylmagnesium/tri-
ethylaluminum complex with n-octanol to form another
complex which is treated with titanium tetrachloride.
:
:.
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--2--
U.S. 3,642,746 discloses complexing of anhydrous
metal halides with alcohols prior to reaction with titanium
tetrachloride. The resulting catalysts are used for
~-olefin polymerization.
U.S. 4,170,567 discloses the reaction product of
titanium tetrachloride with an alcohol which then is reacted
with a magnesia to provide a polymerization catalyst.
U.S. 4,105~585 discloses a process for making a
Ziegler catalyst by reacting magnesium metal and a halogen-
containing titanium compound in the presence of an alcohol.
U.S. 4~087~380 is similar to U.S. 4,105,585
e~cept that the components are deposited on magnesia.
Summary of the Invention
When used in a particle form process for the poly-
merization of ethylene, the catalyst, in conjunction with
a cocatalyst and hydrogen, displays exceptional resin melt
index control and is capable of producing resins with a
wide melt index range from fractional high load to 50 g/10
minutes or more at unpredicted and surprisingly e~cellent
productivity and with resin particle size and form with
minimal fines. An extrudate of this resin displays low
brittleness and ~ood 1exibility.
Resins of this type are particularly useful
for injection molding or as a bl~nding component with
high molecular weight polyethylene for applications such
as film, etc.
This invention relates to improved supported type
catalysts for the polymerization of ~-olefins, especially
ethylene.
The catalyst is prepared by (1) reacting a finely
divided, difficultly reducible, porous support with
(2) a Group II~ organometallic compou~d essentially free
of aluminum alkyls, then reacting the resulting product
with (3) water or a hydrocarbyl alcohol in a molar ratio
to the compound of step (2) of from 0.5 to 1 to 4 to 1,
then reactiny the product of this with (4) a Group IVB
and/or VB transition metal halide ox oxyhalide, (5) removing
essentially all unreacted components and by-products from
the reactions of steps ll), (2), ~3) and (4), followed by
(6) activating the resulting reaction product by treating
. ~
.' ~ '' .
in the substantial absence of air with a cocatalyst that
is either hydroyen or a Group IA, IIA, IIIA or IIB organo-
metallic compound or mixture of two or more of these.
The invention comprehends the catalyst and its
preparation and the method of making polymers of l-olefins
of 2-8 carbon atoms and copolymers of the olefins and
l-olefins of 2-20 carbon atoms comprisin~ polymerizing
the olefins under polymerizing conditions with the catalyst.
More particularly, the porous support may be
selected from the group consisting of alumina, silica,
magnesia, zirconia, or combinations of these such as a
zirconia-silica xerocogel. The preferred support is
alumina or silica. The alumina may be calcined at 1000-
1800F, preferably 1500F; silica preferably at 1100-1300F.
The Group IIA organometallic compounds are
essentially free of aluminum alkyls and are represented
by the general formula MR2, where M may be beryllium,
magnesium, calcium~ strontium or barium, and R is hydrogen
or a hydrocarbyl radical. The preferxed compounds are
dialkylmagnesiums such as dimethylmagnesium, ethyl-n-
butylmagnesium, n-butyl-s-butylmagnesium or di-n-hexylmagnesium.
The dialkylmagnesium compound is first reacted wi~h the
porous supports at a concentration less than, equal to,
or greater than the calcined support's surface hydroxyl
concentration within the following limits:
for silica, the molar ratio of dialkylmagnesium
to the surface hydroxyls is in the range from 0.25 to
1 up to 3.0 to 1 but preferably from 0.5 to 1 up to
2.5 to 1; for alumina, the molar ratio of dialkylmagnesium
to the surface hydroxyls is in the range from 0.5 to 1 up
to 2.0 to 1 but preferably from 0.8 to 1 up to 1.2 to 1.
The reaction is normally, but not necessarily, conducted
in a hydrocarbon slurry at temperatures ~rom ambient to
about 150C, but usually at 90-100C.
I'he hydrocarbyl alcohol is represented by the
formula ROH, where R is a Cl to C20 alkyl, aryl, alkaryl,
radical. Suitable alcohols are me-thanol, isopropanol,
l-butanol, 2-methyl-1-pentanol, mixtures of linear
primary alcohols such as l-dodecanol, l-tetradecanol,
and 1-hexadecanol. In addition, cyclic alcohols such
as cyclobutanol, l-adamantanol, etc.; aromatic hydroxy
compounds such as benzyl alcohol.
The Group IIA organometallic-treated porous
suppor-t is normally treated with the alcohol at ele-
vated temperatures, usually 90-100C, usually, but not
necessarily, in a hydrocarbon slurry. The molar ratio
of the hydrocarbyl alcohol to the alkylmagnesium on
the porous support is critical and is in the range
from 0.5 -to 1 up to 4 to 1 but preferably from 0.8
to 1 up to 1 to 1. When the molar ratio of hydrocarbyl
alcohol to alkylmagnesium is varied to as high as 3
to 1, the molar concentration of the transition metal
compound must be equal to or greater than the molar
concentration of hydrocarbyl alcohol but preferably
in a 1:1 molar ratio.
Excess hydrocarbyl alcohol, if any, should not
be removed from the composite prior to reaction with
the transition metaI compound. Indeed, if it is
removed, reactivity of the catalyst is reduced.
Group IVB or VB transition metal compounds are
halides or oxyhalldes of these ~etals, the preferred
compound being titanium tetrachloride. It is reacted
with the composite containing the alkylmaynesium com-
pound in a molar ratio of transition metal compound
to alkylmagnesium compound in the range from 0.5 to 1
up to 4 to 1, but preferably from 0~8 to 1 up to 1:1.
The reaction usually takes place in a hydrocarbon
slurry at temperatures in the range 90-150C, espe-
cially in the range, 90-135C. The Group IVB and/or
VB transition metal compound may also be used neat,
in which case the desirable reaction temperature is
usually about 135C.
7~
Finally, all unreacted components and by-prod-
ucts are removed if necessary by dry hydrocarbon wash-
ing or by dry inert gas fluidization at temperatures
up to about 150C but preferably at temperatures below
100C.
Activation of the solid catalyst takes place
in the essential absence of oxygen with a cocatalyst
selected from the Group IA, IIA, IIIA, and/or IIB
organometallic compounds including hydrogen. Examples
are n-butyllithium, diethylmagnesium, triisobutylalu-
minum, diethylaluminum chloride, diethylzinc, etc.
The molar ratio of the cocatalyst to the Group IVB
and VB transition me-tal can be from 0.1:1 to 10:1,
preferably about 3:1.
Polymerization of ethylene took place under
two sets of conditions, each using triisobutylaluminum
as cocatalyst. Pressure bott]e (PB) conditions are
500 cc _-heptane as diluent, 35 psig ethylene added
on demand and at about 140F. Particle form (PF)
20 conditions are 2900 cc isobutane as diluent, 550 psig
total pressure with ethylene, and at 220F. The
abbreviation BEM stands for ethyl-n-butylmagnesium.
Description of the Preferred Embodiments
All catalyst data presented in Examples 1 through
39 are presented in the Table.
Comparative Examples 1 -to 4 inclusive show
that the absencè of a dialkylmagnesium compound and
a hydrocarbyl alcohol or the absence of a hydrocarbyl
alcohol, or the absence of a dialkylmagnesium compound
gives rise to catalysts with poor activity.
Example 1
Under N2, 10 g of silica calcined at 1300F
(surface area, 300 m /g; N2 pore volume, 1.7 cc/g)
was mixed wi.th 50 cc TiC14. The mixture was stirred
and heated for one hour at 125-130C. The product was
then collected under N2, washed with pure _ hexane
and dried. The final dry product contained 3.5 wt.%
titanium. Ethylene polymerization under PB conditions
showed poor activity at 20 g/g cat/hr.
Exam~le_
A simi]ar catalyst was prepared as described
in Example 1 except alumina calcined at 1300F (sur-
face hydroxyl concentration, 0.96 mmoles/g; surface
10 area, 371 m /g; H2O pore volume, 1.8 cc/g) was used
in place of silica. A product containing 3.9 wt.
titanlum was ~btained. Although the reactivity of
this catalyst was four times greater than the corres-
ponding catalyst based on silica, its activity was
still considered low at 87 g/g cat/hr under PB (Pres-
sure Bottle) conditions.
Example 3
Under ~2' 20 g of alumina calcined at 1500F
was mixed with 120 cc pure n-heptane. Twenty-nine cc
of a 10 wt.% solution of BEM in n-heptane was then
added. The mixture was stirred and heated under reflux
for one hour. Without cooling, 1.8 cc of TiC14 was
added and the mixture heated for an additional hour.
The product was collected, washed with n-hexane, and
dried under N2. Analysis showed 2.8 wt.% titanium.
Under PB conditions, activity was poor at 65 g/g cat/
hr.
Example 4
A catalyst prepared with 1500F alumina in the
usual manner with l-butanol and TiC14 but without a
dialkylmagnesium compound showed no activity.
Invention Examples 5 to 11 inclusive cover the
support type. Results show that a variety of silicas
and aluminas can be used. Examples 5, 8, 9, 10 and 11
,, ,
,
represent catalysts prepared with preferred concen-
trations and ratios of components. Example 11 shows
that no additional hydrocarbon diluent is necessary
during preparation.
E~ample 5
Under N2, 20 g of silica calcined at 1100F
(surface area 300 m /g; N2 pore volume, 1.7 cc/g) was
mixed with 120 cc pure _-heptane. With s-tirring, 71
cc of 10 wt.% solution of BEM in _-heptane was added.
The mixture was heated at 90-100C for one hour.
Without cooling, 3.7 cc of l-butanol was added
to the mixture. Heating continued for an additional
quarter hour a-t 90-100C. Again without cooling,
4.4 cc of TiC14 was added. Heating continued at 90-
100C for an additional hour. Under ~2' the productwas separated from the liquid phase and washed with
n-hexane until free of unreacted ingredients or by-
products. The washing solvent was removed by N2 at
<100C. The final dry product contained 4.0 wt.%
titanium.
Evaluation under PB onditions with triisobutyl-
aluminum as cocatalyst showed that it was quite active
at 142 g/g cat/hr; under PF conditions and`50 psig hy-
drogen, activity was high at 1307 g/g cat/hr. Resin
melt index was 0.5 g/10 minutes; Rd was 3.1 and Sw was
also 3.1, implying narrow molecular weight distribu-
tion and low weight swell.
Example 6
Under N2, 10 g of silica calcined at 1300F,
having the same physical properties as described in
Example 5, was mixed with 60 cc pure _-heptane. With
stirring, 16 cc of 10 wt.% BEM in _-heptane was added.
The mixture was heated at 90-100C for one hour. With-
out cooling, 0.9 cc oE l-butanol was added to the
mixture. Heating was continued for an additional
7~ ~)57
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0.25 hour. Again without cooling, 4.0 cc of TiC14
was added. Heating continued for an additional hour
at 90-100C. Work-up of the product under N2 involved
separation, washing with pure hexane, and drying at
<100C witn N2 to give a cream-colored dry product
containing 4.1 wt.% titanium.
Reactivity under PB conditions was on the low
side at 8~ g/g cat/hr as compared to the reactivity
of the Example 5 catalyst. Activity under PF condi-
tions was good at 1038 g/g cat/hr with 50 psig hydro-
gen. Resin melt index was 0.5 g/10 minutes; Rd and
Sw were 3.7 and 3.5, respectively, again showing a
narrow molecular weight distribution and relatively
low weight swell.
Example 7
This catalyst was prepared exactly as described
in Example 6 except with another type of 1300F calcined
silica. The silica used had a surface area of 430 m2/g
and a water pore volume of 2.1 cc/g. The final cata-
lyst contained 5.9 wt.% titanium.
The catalyst actlvated with triisobutylaluminumgave an activity of 132 g/g cat/hr under PB conditions,
and a reactivity of 1089 g/g cat/hr under PF conditions.
- EIigh load melt index was 1.3 wlth 50 psig hydrogen.
Example 8
Another type of silica with surface area of
300 m2/g and water pore volume of 1.97 cc/g was used
to prepare a catalyst as described in Example 5. A
catalyst containing 4.3 wt.% titanium was obtained.
Activity under PB conditions was good at 141 g/g
cat/hr, but on the low side under PF conditions with
50 psig hydrogen, 333 g/g cat/hr. Resin melt index
was very high at 56 g/10 minutes.
Exam~
In place of silica, an alumina with surface
area of 250 m2/g, water pore volume of 0.55 cc/g, and
apparent bulk density of 0.8 g/cc, was used to prepare
a near optimum catalyst as follows. Under N2, 20 g of
the alumina calcined at 1500F was mixed with 120 cc
pure _-heptane. Twenty-four cc of 10 wt.% ~EM in n-
heptane was added to the mixture which was then stirredand heated at 90-100C for one hour. l-Butanol, 1.2cc,
was then added to the hot mixture. Heating at 90-100C
was continued for an additional 0.25 hour after which
1.5 cc of TiC14 was added followed by continued heating
for one hour. The usual work-up gave a dry catalyst
containing 3.3 wt.% titanium. Evaluation under PB con-
ditions showed good activity at 147 g/g cat/hr; under
PF conditions, activity was fair at 318 g/g cat/hr
with 50 psig H2-
Example 10
Two hundred g of a 1500F calcined alumina wi-th
surface area of 371 m2/g; pore volume of 1.8 cc/g;
surface hydroxyl concentration of 0.96 mmoles/g and ap-
parent bulk density of 0.28 g/cc was mixed under N2
with 600 cc pure n-heptane. With stirring, 286 cc
of 10 wt.% BEM in n-heptane was adcled. The mixture
was heated at 90-100C for one hour. Fourteen cc of
l~butanol was then added to the hot mixture followed
by continued heating for 0.5 hour. Then 18 cc of
TiC14 was added and the mixture heated an additional
hour at 90-100C. The usual work-up provided a product
containing 3.2 wt.% titanium and 9.3 wt.% chloride.
Pressure bottle conditions with triisobutylalu-
minum as cocatalyst revealed a high reactivity of
166 g/g cat/hr; PF evaluation showed an activity of
1821 g/g cat/hr with the same cocatalyst and with
50 psig hydrogen as modifier. High load resin melt
index was 0.24.
Fxample 11
-
Twenty g of the same alumina described in Exam-
ple 10 was placed under N2, mixed with 29 cc of 10 wt.%
--10--
BEM in _-heptane and heated for 0.25 hour at 90-100C.
Then 1.6 cc l-butanol was added and the mixture stirred
and heated for an additional 0.25 hour. Without cool-
ing, 1.8 cc of TiCl~ was added directly into the
stirred mixture. The N2 flow was then raised to remove
the _-heptane associated with the alkylmagnesium. The
final dry product contained 3.0 wt.% titanium.
Evaluation under PB conditions showed a high
reactivity of 200 g/g cat/hr with triisobutylaluminum
as cocatalyst. Modification with 50 psig H2 under PF
conditions showed an activity of 533 g/g cat/hr.
Resin melt index was 3.2 g/l0 minutes; Rd was 6.6 and
Sw was 4.5.
Invention Examples 12 to 17 inclusive illustrate
that a variety of pure or mixed hydrocarbyl alcohols
can be used but that primary alcohols rather than
secondary alcohols are preferred.
Example 12
This catalyst has been described by Example 10
and S}IOWS that l-butanol, a primary straight chain
aliphatic alcohol, gave a high act:ivity catalyst
especially when the preferred concentration of com-
- ponents is used for the particular alumina support.
Example 13
A secondary aliphatic alcohol was used to pre-
pare the catalyst of this example. Under N2, 10 g of
1500F calcined alumina (described in Example 10) was
mixed with 60 cc of pure n-heptane and then with 16 cc
10 wt.% solution of BEM in _-heptane. The mixture
was stirred and heated 0.5 hour at 90-100C. With-
out cooling, 0.9 cc of 2-butanol was added and the
heating continued for an additional 0.25 hour. Four cc
of TiC14 was then added followed by heating at 90-100C
for one hour. ~he usual work up gave a catalyst con-
taining 6.8 wt.% titanium.
~-~'7~
With triisobutylaluminum as cocatalyst, the
catalyst showed an activity of 28 g/g cat/hr, under
PB conditions.
Example l
A similar catalys-t to Example 13 was prepared
with changes only in the concentratlons of ingredients.
Thus, 20 g of 1500F calcined alumina (described in
Example 10) was mixed with 120 cc pure _-heptane and
29cc of 10 wt.% BEM in n-heptane. The mixture was
stirred and heated one hour at 90-100C. Again with-
out cooling, 1.6 cc 2-butanol was added and allowed
to react 0.25 hour followed by the addition of 1.8 cc
TiC14 and an additional one hour of heating. Work-up
gave a catalyst containing 2.6 wt.% titanium.
As with the catalyst of example 13, an activity
of 51 g/g cat/hr was observed under P~ conditions.
Example 15
A mixture of C6, C8, and C10 primary straight
chain hydrocarbyl alcohols with average molecular
weight of 149 was used to prepare this catalyst by the
method of Example 14. In place of the 2-butanol,
215 cc-of the alcohol mixture was used to produce a
catalyst containing 3.2 wt.% titanium.
The catalys-t showed good activity at 93 g/g
cat/hr under PB conditions and a high activlty of 1031
g/g cat/hr with 50 psig H2 under PF conditions. Tri-
isobutylaluminum was ~he cocatalyst.
Example 16
A primary aralkyl alcohol may be substituted
for a primary straight chain aliphatic alcohol as
shown by this example. The catalyst was prepared
by the method o~ Example 13 except that 1 cc of benzyl
alcohol was used in place o 2-butanol to give a
catalyst containing 4.8 wt.% titanium.
o~
-12-
~ hlgh activity of 100 g/g eat/hr was observed
under PB conditions; under PF eonditions with 20 psiy
H2, activity was somewhat low at 202 g/g cat/hr.
Example 17
Methanol, the lowest molecular weight alcohol,
was used in place of 2-butanol in Example 14. The
catalyst obtained contained 3.6 wt.% titanium.
High PB aetivity at 105 g/g eat/hr was attained
with triisobutylaluminum as cocatal~st; under PF eon- -
ditions with 100 psig H2, activity was 201 g/g cat/hr.
Resin melt index was high at 14 g/10 minutes.
Examples 18 to 21 inelusive show that the alco-
hol concentration can be increased to as high as three
equivalents to one equivalent of alkylmagnesium without
lS reducing eatalyst aetivity as long as the eoncentration
of TiC14 added remains greater than the aleohol con-
eentration. Eaeh example was prepared with 1500F
ealcined alumina having the physical properties de-
scribed in Example 10 and with l-butanol as the alcohol.
Only the coneentration of the alcohol was increased;
the eoneentration of TiC14 remained in exeess over the
aleohol. Triisobutylaluminum was used as eoeatalyst.
Example 18
Under N2, 10 g of alumina was mixed with 60 ee
pure _-heptane and 16 ee 10 wt.% BEM in n-heptane. The
mixture was stirred and heated one hour at 90-100C.
Then 0.9 ee l-butanol was added and allowed to react
0.25 hour. While hot, 4 ee TiC14 was added, the heat-
ing continued for an additional hour at 90-100C.
The usual work-up gave a eatalyst containing 4.5 wt.%
titanium.
The eatalyst showed high aetivity at 182 g/g
eat/hr under PB eonditions and 662 g/g eat/hr under PF
eonditions with 50 psig H2. Resin rheological proper-
ties were 0.2 g/10 minutes mel-t index, 4.5 Rd and3.8 Sw.
-13-
Example 19
The catalyst was prepared by the method of
Example 18 except 1.4 cc 1 butanol and 3.3 cc TiC14
were used to give a catalyst containing 7.0 wt.%
titanium.
Again, activity was high and nearly identical
to tha-t of Example 18 at 181 g/g cat/hr under Ps con-
ditions. An activity of 744 g/g cat/hr with 50 psig
H2 was attained under PF conditions. Resin properties
were 1.0 g/10 minutes melt index, 4.5 Rd and 4.4 Sw.
Example 2Q
Preparation was by the method of Example 18
except that 1.8 cc l-butanol and 3.3 cc TiC14 was
used to give a catalyst with ~.5 wt.% titanium.
Pressure bottle evaluation again showed a high
activity at 226 g/g cat/hr; PF conditions with 50 psig
H2 showed high activity at 727 g/g cat/hr. High load
melt index of the resin was 2.1 g/10 minutes.
Example 21
The final catalyst of this series was again
prepared according to Example 18 except that 2.7 cc
l~butanol and 4 cc TiC14 were used to prepare the
cataIyst which contained 6.2 wt.% titanium.
Again, a high activity catalyst, 203 g/g cat/
hr, was obtained despi-te the high concentration of
l~butanol. Under PF conditions and 50 psig H2, activ-
ity was high at 1422 g/g cat/hr. Resin properties
were 0.3 g/10 minutes melt index, 3.3 Rd and 3.4 Sw.
~xamples 22 and 23 show that poor activity
catalysts are obtained when the alcohol concentration
is increased or decreased while the concentrations
of ethyl-n butylmagnesium and TiC14 remain unchanged
for the particular alumina used. Both examples employ
l-butanol. Again, triisobutylaluminum was the cocata-
lyst.
73 C~
-14-
Example 22
Under N2, 20 g of 1500F calcined alumina tde-
scribed in Example 10) was mixed with 120 cc pure
n-heptane and 20 cc 10 wt.% in n-heptane. The mixture
was stirred and heated at 90-100C for one hour, fol-
lowed by the addition of 4.9 cc (twofold excess) of
1 butanol. Heating was continued for 0.25 hour fol-
lowed by the addition of 1.8 cc TiC14 and continued
heating for one hour~ Following the usual work-up,
a catalyst was obtained which contained 1.7 wt.~ ti-
tanium.
Activity under PB conditions was very low at
7 g/g cat/hr.
Example 23
This catalyst was prepared by the method of
Example 22 except for a twofold decrease in the 1-
butanol (0.5 cc) concentration.
Again, PB activity was low at 60 g/g cat/hr.
Examples 24 to 26 inclusive show that departure
from the preferred concentrations of components for
the particular alumina support used (described in
Example 10) leads to catalysts with poor activity.
- The preferred catalyst based on this particular alumina
is represented by Example 12 or 29.
Example 24
Under N2,~20 g 1500F calcined alumina was
mixed with 120 cc pure n-heptane and 24 cc 10 wt.% BEM
in n-heptane. The mixture was heated and stirred
one hour at 90-100C after which 1.2 cc of l-butanol
was added. Heating was continued for 0.25 hour fol-
lowed by addition of 1.45 cc TiC14 and continued heat-
ing for one hour.~ The usual work-up gave a catalyst
containing 3.9 wt.% titanium.
Evaluation under PB conditions indicated poor
activity at 55 g/g cat/hr.
-15-
Example 25
A similar catalyst was prepared by the method
of Example 24 except -that 29 cc of 10 wt.~ BEM in
n-heptane, 0.8 cc 1-butanol, and 1.0 cc TiC14 was used
to give a catalyst containing 2.1 wt.% titanium.
Again, activity was low at 16 g/g cat/hr under
PB conditions.
Example 26
The final catalyst was prepared by the method
of Example 24 except 14 cc 10 wt.% BEM in n-heptane,
0.8 cc l-butanol, and 1.0 cc TiC14 was used to give a
catalyst containing 2.0 wt.% titanium.
Activlty under PB conditions was again low at
37 g/g cat/hr.
Examples 27 and 28 represent catalysts which
were purposely overloaded with alkylmagnesium, 1-
butanol, and Ti.C14 simultaneously in terms of the con-
centration of the alumina support's surface hydroxyl
concentration described in Example 10. ~lthough cata-
lyst activity was increased, performance in terms
of reactor fouling was poor.
Example 27
Under ~2~- ~ g of 1500F calcined alumina was
mixed with 120 cc pure n-heptane and 48 cc 10 wt.%
BEM in n-heptane. The mixture was stirred and heated
for one hour at 90-100C. Whlle hot, 2.4 cc l-butanol
was added. Heating contlnued an addltional 0.25 hour.
~hen 2.9 cc TiC14 was added. Heating continued for
one hour. The usual work-up gave a catalyst contain-
- 30 ing 3.4 wt.% titanium.
Evaluation under PB conditions showed a very
high activity of 232 g/g cat/hr; under PF conditions
with 50 psig H2, activity was 844 g/g cat/hr with
reactor fouling. Resin melt index was 0.1 g/10 min-
utes; Rd and Sw were 3.0 and 3.3, respectively.
-16-
Example 28
This catalyst was prepared as described by
Example 27 except 10 g of alumina, 32 cc 10 wt.% BEM
in n-heptane, 1.8 cc l-butanol, and 8 cc TiC14 were
used to give a catalyst containing 4.2 wt.% titanium.
Pressure bottle evaluation showed very high
activity at 330 g/g cat/hr under PB conditions. The
resin produced contained up to 14 wt.% flake resin,
suggesting a high potential for reactor fouling.
Examples 29, 30 and 31 illustrate the sensitiv-
ity of these catalysts to hydrogen concentration as
reflected in the melt index of the resin produced.
Example 30 especially shows that under eontinuous PF
reaetor conditions in a pilot plant, resin with melt
index as high as 30.7 can be produced easily.
Example 29
The catalyst was prepared with alumina aecording
to the method of Example 10 except on a smaller scale
to give a catalyst containing 2.9 wt.% titanium.
~igh activity was observed under PB conditions
at 178 g/g cat/hr. Testing under P~ conditions at
varying hydrogen concentrations revealed the following
e~fect on resin melt index:
Hydrogen Catalyst
25Concentration, Resin Productivity
psig ~elt Index g/g cat
none Less than 2148
high load
0.3 high load 1798
30 75 3.3 high load 2765
100 21 1250
100+ 54 1128
7~
-17-
xample 30
This catalyst was prepared with alumina as
support on a seale twenty times that of Example 18
for use in a pilot plant continuous particle form
reactor to produce high melt index resin. The eatalyst
contained 9.4 wt.% -titanium and 11 wt.% chloride.
Under continuous particle form conditions at
224F, 1.15 mol% hydrogen, 3.9 wt.% ethylene concen-
tration, and continuously fed triisobutylaluminum as
cocatalyst, a productivity level up to 3500 g/g cat
10 was attained. Resin melt index was 30.7 g/10 minutes,
bulk density was 29.3, and particle size greater or
equal to 60 mesh was 58.5%.
Example 31
This example also illustrates the sensitivity
of a similar catalyst based on siliea to hydrogen eon-
centration as reflected in the melt index of the resin
produced. The catalyst was prepared aecording to
Example 5.
Hydrogen Catalyst
20Concentration,ResinProdue-tivity
psig Melt Index_ g/g cat
None I,ess than 353Z
- high load
0.5 1960
~2 982
100 92 2504
Examples 3Z to 36 illustrate that melt index
eontrol of resulting polymers and eopolymers ean in
part be achieved by adjusting the coneentrations of
catalyst components on the support while maintaining
a eonstant molar ratio between them. As a result,
polymers and copolymers ean be produeed within a pre-
seleeted mel~ index range with minimum hydrogen con-
-18-
centration thus avoiding a reduction in catalyst pro-
ductivity. Under a given set of polymer synthesis con-
ditions, the catalyst of Example 32 is capable of
giving a melt index in the range from fractional high
load to about 0.5; Example 34, from fractional high
load to about 4; Example 34, from high load to about
23; Example 35, from high load to about 14; Example
36, from fractional to about 7.6.
All catalysts were prepared under N2 in an iso-
butane media with 1100F calcined silica with a surface
area of 300 m2/g and a N2 pore volume of 1.7 cc/g, with
ethyl-_-butylmagnesium, l~butanol, and titanium tetra-
chloride at the concentrations indicated in the Table.
The molar ratios of l-butanol to BEM, TiC14 to l-buta~
15 nol, and TiC14 to BEM were held constant at 0.88,
1 and 0.88 respectively. The final catalysts were
dried with N2 at 200-220F. Each was then tested under
particle form conditions in a one gallon bench scale
autoclave with varying hydrogen concentrations. Re-
sults are presented in the Table, below.
,
:: : : :
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--19--
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-20-
Example 37
This example illustrates a critical feature of
the catalyst preparation. In order to provide a cat-
alyst of high reactivity, the hydrocarbyl alcohol
5 must no-t be removed from the dialkylmagnesium/support
composite prior to reaction of the mixture with a
transition metal compound.
Thus, under N~, 200 g of 1300E calcined alumina
was mixed with 600 cc n-heptane. Three hundred eighteen
cc of a 10 wt.% solution of BEM in n-heptane was added.
The mixture was stirred and heated for two hours at
90-100C. While hot, 55 cc of l-butanol was added.
Heating was continued while the N2 flow was incxeased
in order to completely remove the l-butanol and n-
heptane by evaporation. The product was finally
placed under vacuum to lnsure complete removal of
the l-butanol. The final product was an off-whlte
flowable powder.
A 5 g portion of the product was mixed with
25 cc n-heptane under N2. Exactly 0.25 cc l-butanol
was added and allowed to mix 0.25 hour. One cc titan- '~
lum tetrachloride was added and the mixture stirred and
heated at 90-100C for one hour. After cooling, the
slurry was filtered under N2, washed with n-hexane,
and dried under N2. ~ctivation of the catalyst con-
taining 4.2 wt.% titanium with triisobutylaluminum
in the usual manner gave rise to a poor catalyst under
PB conditions. Activity was only 42 g/g catjhr.
Example 38
Completely removing the alcohol, as described
ln the exarnple above, and not reading it prlor to
reaction with titanium tetrachloride is illustrated
by this example.
Under N2, 170 g of the alcohol-free l-butanol-
treated ethyl-n-butylmagneslum-alumlna composite pre-
pared as described in Example 32, was mixed with
-21-
1000 cc n-heptane. Thirty-four cc of titanium -tetra-
chloride was added. The mixture was stirred and heated
two hours at 95-100C, cooled, filtered, washed with
_-hexane, and dried under N2. A product containing 3.9
wt.% titanium was obtained.
Activation of this product with triisobutylalu-
minum led to a poor catalyst as tested under PB condi-
tions. Activity was only 34 g/g cat/hr.
Example 39
The effect on catalyst activity as a result of
using butoxytitanium trichloride as the titanium source
added to the alcohol-free l-butanol-treated ethyl-n-
butylmagnesium on alumina composite prepared as de-
scribed in Example 32 is illustrated by this example.
To a 5 g portion of the alcohol-free product
from Example 32 in 25 cc n-heptane was added an n-hep-
tane solution of the reaction product, 0.45 cc 1-
butanol and 0.55 cc titanium tetrachloride. The mixture
was s-tirred under N2 and heated for one hour at 90-
100C. The mixture was cooled, the product filtered,
washed with n-hexane, and dried under N2. The product
contained 2.5 wt.% titanium.
The product activated with triisobutylaluminum
showed an activity of only 19 g/g cat/hr under PB con-
ditions.
--22--
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-32-
FOOTNOTES TO TABLE
a~ Ethyl-n-butylmagnesium
b) Hydrocarbyl alcohol
c) Pressure bot-tle conditions: 500 cc n-heptane, 35 psig
ethylene pressure fed on demand and 140r'F
d) Triisobutylaluminum used as cocatalyst
e) Particle form conditions: 2900 cc isobutane, 550 psig
total pressure, and 220F
f) Surface area, 371 m2/g; H2O pore volume, 1.8 cc/g;
surface hydroxyl concentration, 0.96 mmoles/g
g) Rd is a measure of the molecular weight distribution
as defined by M. Shida and L. V. Cancio, Polymer Engin-
eering and Science, March, 1971, Vol. II, Mo. 2; Sw is
weight swell as defined by Cancio, L. V., and Joyner, R.S.,
Modern Plastics, January, 1977. MI is melt index deter-
mined according to ASTM D1238-62, condition F.
h) A mixture of 3.3 wt.~ l-hexanol, 42.5 wt.% l-octanol,
and 53.8 wt.% l~decanol
i) Surface area, 300 m2/g; N2 pore volume, 1.7 cc/g
j) Surface area, 420 m2/g; H2O pore volume, 2.1 cc/g
k~ Continuous particle form conditions of 224F, 1.16 mol%
hydrogen, 3.9 wt.% ethylene concentration, and continuously
~ed triisobutylaluminum as cocatalyst. Resin melt index
was 30.7 g/10 minutes, bulk density was 29.3, and resin
particle size greater or equal to 60 mesh was 58 5%.
l) Alcohol totally removed and then readded prior to TiC14
m~ Alcohol totally removed and not readded prior to reaction
with TiC14
n) n-Butoxytitanium trichloride was added to the alcohol-free
composite
o) Surface area, 300 m2/g; N2 pore volume, 1.97 cc/g
p) Surface area, 250 m2/g; H2O pore volume, 0.55 cc/g
